CN102558812A - Polycarbonate resin composition and molded article using the same - Google Patents
Polycarbonate resin composition and molded article using the same Download PDFInfo
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- CN102558812A CN102558812A CN2011103143639A CN201110314363A CN102558812A CN 102558812 A CN102558812 A CN 102558812A CN 2011103143639 A CN2011103143639 A CN 2011103143639A CN 201110314363 A CN201110314363 A CN 201110314363A CN 102558812 A CN102558812 A CN 102558812A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
The present invention relates to a polycarbonate resin composition and a molded article using the same. The polycarbonate resin composition having high gloss and impact resistance and good surface properties including 100 parts by weight of a base resinincluding a polycarbonate resin (A) and a polycarbonate-polysiloxane copolymer (B); and 0.1 to 10 parts by weight of polyalkylaryl siloxane (C) having a refractive index of 1.42 to 1.59. The composition exhibits high gloss and blackness and has excellent impact resistance, heat resistance and light resistance, and superior mar resistance, which is resistance to fine scratches, and thus it is properly used for non-coating products.
Description
Technical field
The present invention relates to have the poly carbonate resin composition of high gloss and shock resistance and good surface properties, and with the moulded product of said composition.More specifically, the present invention relates to have the poly carbonate resin composition of high gloss and shock resistance, and with the moulded product of said composition, said compsn keeps transparency minimize surface friction simultaneously, to have excellent anti-damageability, promptly anti-fine scratch property.
Background technology
Polycarbonate resin has excellent hardness, shock resistance, thermostability, self-extinguishing, dimensional stability and thermotolerance, thereby is used for Electrical and Electronic element, automotive components, camera lens, and is used as the substitute of glass.Yet, being used for the transparent product of requirement, the scratch resistance of polycarbonate resin is not so good as glass, and is exposed to sunlight flavescence of following time for a long time.
Therefore, suggestion with polycarbonate resin with have an excellent scratch resistance gather (TEB 3K) (PMMA) method of blend.Yet because the significant difference of specific refractory power between consistency difference and polycarbonate resin and the PMMA resin, their rafting is opaque and on outward appearance, shock resistance and scratch resistance, have inferior quality.
Recently, independent coating process is used to provide scratch resistance and high gloss texture.Yet this coating process requires a plurality of steps, produces defective and toxic volatile component, and increases production cost.
In order to address the above problem, developed uncoated material.As uncoated material, need this material can realize inherent high gloss texture and inherent scratch resistance.Yet also untapped all these desired properties of having provided are like the resin of color rendition property, shock resistance, thermotolerance and scratch resistance.
Contriver of the present invention developed comprise polycarbonate resin, polycarbonate-polysiloxane and modification (methyl) PEMULEN TR2 resin combination to address the above problem.Yet this resin combination is satisfactory aspect scratch resistance, chemical-resistant and shock resistance, but has relatively poor anti-damageability, and promptly anti-fine scratch property is poor.Thereby this resin combination has limitation in the application of the element that is used for frequent touch or pollution.
Therefore, need exploitation realize the high gloss texture inherently, have common scratch resistance and anti-damageability is anti-fine scratch property, and present the uncoated material of excellent shock resistance, photostabilization, thermotolerance and chemical-resistant.
Summary of the invention
One aspect of the present invention provides a kind of the have high gloss of good surface properties and the poly carbonate resin composition of high impact properties.Said compsn has excellent scratch resistance and excellent anti-damageability, and demonstrates the high gloss texture and keep the transparency simultaneously.Said compsn comprises the matrix resin that polycarbonate resin (A) and polycarbonate-polysiloxane copolymer (B) of 100 weight parts; And the polyoxyethylene alkyl aryl radical siloxane (C) with specific refractory power of 1.42 to 1.59 of 0.1 to 10 weight part.
Said polyoxyethylene alkyl aryl radical siloxane (C) can have the weight-average molecular weight of 400g/mol to 1000g/mol.
Polyoxyethylene alkyl aryl radical siloxane (C) can have the viscosity of 20mPa.s to 120mPa.s under 25 ℃.
In one embodiment, said matrix resin can comprise the said polycarbonate resin (A) of 1wt% to 99wt% and the said polycarbonate-polysiloxane copolymer (B) of 1wt% to 99wt%.
In another embodiment, said polycarbonate-polysiloxane copolymer (B) can comprise 1 to 99wt% polycarbonate block and 1 to 99wt% polysiloxane block.
Said matrix resin can further comprise 40wt% or modification still less (methyl) acrylic copolymer resin.Said modification (methyl) acrylic copolymer resin can have 1.495 to 1.590 specific refractory power.
Said modification (methyl) acrylic copolymer resin can have the weight-average molecular weight of 5000g/mol to 50000g/mol.
Said modification (methyl) acrylic copolymer resin can be aromatics or alicyclic (methyl) acrylic ester polymer.
Said modification (methyl) acrylic copolymer resin can be the polymkeric substance of the simple function group unsaturated monomer (D2) of the aromatics that comprises 20wt% to 100wt% or alicyclic (methyl) propenoate (D1) and 0 to 80wt%.
Said simple function group unsaturated monomer (D2) can comprise and is selected from least a in the group of being made up of ester, acid amides, nitrile, glycidyl allyl ether, SY-Monomer G and the styrene monomer of (methyl) propenoate, unsaturated carboxylic acid, acid anhydrides, hydroxyl.
In one embodiment, said poly carbonate resin composition can further comprise the fatty acid amide surface treatment agent.Based on the said matrix resin of 100 weight parts, the content of said fatty acid amide surface treatment agent can be 0.1 to 5 weight part.
In one embodiment, said poly carbonate resin composition can further comprise syndiotactic PS.Based on the said matrix resin of 100 weight parts, the content of said syndiotactic PS can be 5 weight parts or still less.
Said resin combination can further comprise additive; Like antiseptic-germicide, thermo-stabilizer, inhibitor, releasing agent, photostabilizer, inorganic additives, tensio-active agent, coupling agent, softening agent, mixture (admixture), stablizer, lubricant, static inhibitor, toning agent, flame-proofing agent, weather resisting agent, tinting material, UV absorption agent, UV blocking agent, fire retardant, filler, nucleator, adhesion auxiliary agent and tackiness agent, they can use separately or use with mixture.
Said poly carbonate resin composition can have 80% or higher total transmittance, 10.0 or littler opacity and 28 or littler blackness (Lb).
Another aspect of the present invention provides the moulded product of the said poly carbonate resin composition of a kind of usefulness.
Description of drawings
By detailed description below in conjunction with accompanying drawing, of the present invention above will become obviously with others, feature and advantage, wherein:
Fig. 1 is according to the photo after the die orifice Impact Test in the sample of embodiment 4 and Comparative Examples 4.
Embodiment
Below will be with reference to accompanying drawing detailed description exemplary embodiment; Yet they can multi-formly be implemented, and do not should be understood to restriction the present invention.On the contrary, provide these embodiments to make the disclosure, and scope of the present invention is all conveyed to those skilled in the art complete and complete.
Unless otherwise mentioned, " (methyl) propenoate " comprises " propenoate " and " methacrylic ester " jointly in the literary composition.
In addition, unless otherwise mentioned, " replacement " is meant the Wasserstoffatoms of compound by halogen atom, like F, Cl, Br and I; Hydroxyl; Nitro; Cyanic acid; Amino; Azido-; Amidino groups; Diazanyl; Hydrazono-; Carbonyl; Carbamoyl group; Sulfydryl; Ester group; Carboxyl or its salt; Sulfonic group or its salt; Phosphate-based or its salt; C1 to C20 alkyl; C2 to C20 thiazolinyl; C2 to C20 alkynyl; C1 to C20 alkoxyl group; C6 to C30 aryl; C6 to C30 aryloxy; C3 to C30 naphthenic base; C3 to C30 cycloalkenyl group; C3 to C30 cycloalkynyl radical; Or the substituting group of their combination replaces.
One side of the present invention provides a kind of poly carbonate resin composition that comprises polycarbonate resin (A), polycarbonate-polysiloxane copolymer (B) and polyoxyethylene alkyl aryl radical siloxane (C).
Matrix resin comprises the resin Composition except that polyoxyethylene alkyl aryl radical siloxane (C).
In one embodiment, matrix resin can comprise polycarbonate resin (A) and polycarbonate-polysiloxane copolymer (B).
In one embodiment, matrix resin can comprise polycarbonate resin (A), polycarbonate-polysilane copolymers (B) and modification (methyl) acrylic copolymer resin (D).
Below will specify each component.
(A) polycarbonate resin
Polycarbonate resin can prepare through diphenol and phosgene, haloid ether, carbonic ether or their composite reaction by general formula 1 expression.
[general formula 1]
Wherein A representes singly-bound, or halo alkylidene group, replacement or the unsubstituted C5 to C6 of the alkylidene group of replacement or unsubstituted C1 to C30 straight or branched, replacement or unsubstituted C2 to C5 alkenylene, replacement or unsubstituted C2 to C5 alkylidene, replacement or unsubstituted C1 to C30 straight or branched encircle alkylidene group, replacement or unsubstituted C5 to C6 and encircle alkylene oxide group, hydracid ester group, carbonate group, CO, S or the SO2 that alkenylene, replacement or unsubstituted C5 to C10 encircle alkylidene, replacement or unsubstituted C6 to C30 arylidene, replacement or unsubstituted C1 to C20 straight or branched; R1 and R2 are identical or different, and represent replacement or unsubstituted C1 to C30 alkyl or replacement independently or do not replace C6 to C30 aryl; And n1 and n2 represent 0 to 4 integer separately.
Polycarbonate resin can have the repeating unit of at least two kinds of diphenol of combination general formula 1 expression.The instance of above-mentioned diphenol can comprise quinhydrones, Resorcinol, 4,4 '-dihydroxybiphenyl, 2, two (4-phenylor) propane (dihydroxyphenyl propane), 2 of 2-; Two (4-the phenylor)-2-methylbutanes of 4-, two (4-phenylor) methane, 1, two (4-phenylor) hexanaphthenes, 2 of 1-, two (the 3-chloro-4-phenylor) propane, 2 of 2-; 2-two (3; 5-dimethyl--4-phenylor) propane, 2, two (3, the 5-two chloro-4-phenylor) propane, 2 of 2-; Two (3, the 5-two bromo-4-phenylor) propane of 2-, two (4-phenylor) sulfoxide, two (4-phenylor) ketone and two (4-phenylor) ethers.At this, preferably use 2, two (4-phenylor) propane, 2 of 2-, two (the 3-chloro-4-phenylor) propane and 1 of 2-, two (4-phenylor) hexanaphthenes of 1-, and more preferably 2, two (4-phenylor) propane of 2-.
Polycarbonate resin can have 10,000g/mol to 200, the weight-average molecular weight of 000g/mol.In one embodiment, polycarbonate resin can have 15,000g/mol to 80, and the weight-average molecular weight of 000g/mol, but be not limited thereto.
Can the serve as reasons mixture of multipolymer of at least two kinds of diphenol preparation of polycarbonate resin.In addition, polycarbonate resin can comprise linear polycarbonate resin, branched polycarbonate resin and polyester-carbonate copolymer resin.
The instance of linear polycarbonate resin can comprise the bisphenol-a polycarbonate resin.The instance of branched polycarbonate resin can comprise by the polyfunctional group aromatic substance, like trimellitic acid 1,2-anhydride and trimellitic acid, with the compound of diphenol and carbonate reaction preparation.Based on the total amount of branched carbon acid ester resin, the content of polyfunctional group aromatic substance can be 0.05mol% to 2mol%.The instance of polyester-carbonate copolymer resin can comprise the compound that is made by bifunctional carboxylic acid and diphenol and carbonate reaction.The instance of carbonic ether can comprise diaryl carbonate such as diphenyl carbonate, and ethylene carbonate.
Polycarbonate resin can 310 ℃ with 1.2kgf under have 3 to 120g/10min melt flow coefficient (MFI).
Based on the matrix resin of 100wt%, the content of polycarbonate resin can be 1wt% to 99wt%, is preferably 30wt% to 90wt%.In this scope, can obtain the excellent properties balance between shock strength, thermotolerance and the workability.In one embodiment, its content in matrix resin can be 50wt% to 80wt%.
(B) polycarbonate-polysiloxane copolymer
Polycarbonate-polysiloxane copolymer comprises polycarbonate block and polysiloxane block.
The polycarbonate block can comprise by polycarbonate resin (A) deutero-structural unit.
Polysiloxane block can comprise the structural unit by general formula 2 expressions:
R wherein
3And R
4Can be identical or different; And (R and R ' can be identical or different to represent Wasserstoffatoms, replacement or unsubstituted C1 to C20 alkyl, replacement or unsubstituted C2 to C20 thiazolinyl, replacement or unsubstituted C2 to C20 alkynyl, replacement or unsubstituted C1 to C20 alkoxyl group, replacement or unsubstituted C3 to C30 naphthenic base, replacement or unsubstituted C3 to C30 cycloalkenyl group, replacement or unsubstituted C3 to C30 cycloalkynyl radical, replacement or unsubstituted C6 to C30 aryl, replacement or unsubstituted C6 to C30 aryloxy or NRR ' independently; And expression Wasserstoffatoms or replacement or unsubstituted C1 to C20 alkyl); And 2≤m＜10,000.
In general formula 2, m can be in 2 to 10,000 scope.In one embodiment, m can be in 2 to 1000 scope.In this scope, excellent shock resistance can be obtained, and suitable viscosity can be kept, the condition that is suitable for extruding is provided.Particularly, m can be 10 to 100, and preferred 25 to 80.
Polycarbonate-polysiloxane copolymer can comprise 1 to 99wt% polycarbonate block and 1 to 99wt% polysiloxane block.In one embodiment, polycarbonate-polysiloxane copolymer can comprise 40 to 80wt% polycarbonate block and 20 to 60wt% polysiloxane block.In this scope, can obtain excellent shock resistance.In another embodiment, polycarbonate-polysiloxane copolymer can comprise 80 to 95wt% polycarbonate block and 5 to 20wt% polysiloxane block.
Polycarbonate-polysiloxane copolymer can have 10,000 to 30, the weight-average molecular weight of 000g/mol, particularly 15,000 to 22,000g/mol.In this scope, can obtain excellent shock resistance.
But the shock resistance of polycarbonate-polysiloxane copolymer reinforced polycarbonate resin combination because of using modification (methyl) PEMULEN TR2 to reduce.
Based on the matrix resin of 100wt%, the content of polycarbonate-polysiloxane copolymer can be 1 to 99wt%, and preferred 10 to 60wt%.In this scope, can obtain the excellent properties balance between shock strength, thermotolerance and the workability.Particularly, its content can be 20 to 50wt%.In one embodiment, the content ratio between polycarbonate resin (A) and the polycarbonate-polysiloxane copolymer (B) can be 1: 1 to 5: 1, is in particular 1: 1 to 3: 1.
(C) polyoxyethylene alkyl aryl radical siloxane
The polyoxyethylene alkyl aryl radical siloxane is as the surface treatment agent that minimizes friction.Above-mentioned polyoxyethylene alkyl aryl radical siloxane has the repeating unit of general formula 3 expressions:
Wherein R representes to replace or unsubstituted C1 to C6 alkyl, and Ar representes to replace or unsubstituted C6 to C12 aryl.
The polyoxyethylene alkyl aryl radical siloxane can have 1.42 to 1.59, and is preferred 1.47 to 1.59, more preferably 1.49 to 1.59 specific refractory power.In this scope, can obtain the excellent properties balance between the transparency and the anti-damageability.In one embodiment, the polyoxyethylene alkyl aryl radical siloxane can have 1.49 to 1.58, preferred 1.495 to 1.55 specific refractory power.
Polyoxyethylene alkyl aryl radical siloxane (C) can have 400 to 1000g/mol, preferred 600 to 800g/mol weight-average molecular weight.In this scope, diffusion of coloring matter phenomenon (bleed-out phenomenon) can not appear in the surface, and the polyoxyethylene alkyl aryl radical siloxane moves to the surface.
In one embodiment, polyoxyethylene alkyl aryl radical siloxane (C) can have 20 to 120mPa.s under 25 ℃, preferred 30 to 100mPa.s viscosity.In this scope, the surface diffusion of coloring matter phenomenon can not occur, and the polyoxyethylene alkyl aryl radical siloxane moves to the surface.
Polyoxyethylene alkyl aryl radical siloxane (C) can comprise fluid type polyoxyethylene alkyl aryl radical siloxane.
The instance of polyoxyethylene alkyl aryl radical siloxane (C) can include, but are not limited to PSI, polyphenylethyl radical siloxane, gathers the propylbenzene radical siloxane, gathers the butyl phenyl siloxanes, gathers the amylbenzene radical siloxane and gather the hexyl benzene radical siloxane.Particularly, preferably use PSI.
Based on the matrix resin of 100 weight parts, the content of polyoxyethylene alkyl aryl radical siloxane (C) can be 0.1 to 10 weight part.When the content of polyoxyethylene alkyl aryl radical siloxane (C) is less than 0.1wt%, can not obtain enough anti-damageabilities.When the content of polyoxyethylene alkyl aryl radical siloxane (C) during, become muddy greater than 10wt%.Particularly, the content of polyoxyethylene alkyl aryl radical siloxane (C) can be 1 to 7 weight part, for example 1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5 and 7 weight parts.
(D) (methyl) acrylic copolymer resin of modification
Can add (methyl) acrylic copolymer resin (D) of modification to matrix resin.
(methyl) acrylic copolymer resin (D) of modification can be the polymkeric substance of aromatics or alicyclic (methyl) propenoate.In one embodiment, (methyl) acrylic copolymer resin (D) of modification can be the homopolymer of aromatics or alicyclic (methyl) propenoate.In another embodiment, (methyl) acrylic copolymer resin (D) of modification can be the multipolymer of at least two kinds of aromatics of use or alicyclic (methyl) propenoate.In another embodiment, (methyl) acrylic copolymer resin (D) of modification can be aromatics or alicyclic (methyl) propenoate with can with the multipolymer of its monomer polymerized.In another embodiment, (methyl) acrylic copolymer resin (D) of modification can be and uses in above-mentioned modification (methyl) acrylic copolymer resin at least two kinds mixture.
Particularly, (methyl) acrylic copolymer resin (D) of modification can be the polymkeric substance of the simple function group unsaturated monomer (D2) that comprises 20 to 100wt% aromatics or alicyclic (methyl) propenoate (D1) and 0 to 80wt%.More specifically, (methyl) acrylic copolymer resin (D) of modification can be the polymkeric substance of the simple function group unsaturated monomer (D2) that comprises 20 to 99.9wt% aromatics or alicyclic (methyl) propenoate (D1) and 0.1 to 80wt%.In this scope, (methyl) acrylic copolymer resin of modification can have 1.495 or bigger mean refractive index.In one embodiment, (methyl) acrylic copolymer resin (D) of modification can be the polymkeric substance of the simple function group unsaturated monomer (D2) that comprises 25 to 45wt% aromatics or alicyclic (methyl) propenoate (D1) and 55 to 75wt%.
Aromatics or alicyclic (methyl) propenoate (D1) are meant by aromatic substance or alicyclic compound substituted (methyl) acryliccompound.
In one embodiment, aromatics or alicyclic (methyl) propenoate (D1) can have the structure of general formula 4 or 5 expressions.
[general formula 4]
Wherein m representes 0 to 10 integer, and X representes to replace or unsubstituted C6 to C30 aryl, replacement or unsubstituted C3 to C30 naphthenic base, replacement or unsubstituted C3 to C30 cycloalkenyl group or replacement or unsubstituted C3 to C30 cycloalkynyl radical.
In one embodiment, in the group that the optional free ring hexyl of X, phenyl, tolyl, methylethyl phenyl, propyl phenyl, p-methoxy-phenyl, cyclohexyl phenyl, chloro-phenyl-, bromophenyl, phenyl and benzyl phenyl are formed.
[general formula 5]
Wherein m representes 0 to 10 integer, and Y representes oxygen O or sulphur S, and Ar representes to replace or unsubstituted C6 to C30 aryl, replacement or unsubstituted C3 to C30 naphthenic base, replacement or unsubstituted C3 to C30 cycloalkenyl group or replacement or unsubstituted C3 to C30 cycloalkynyl radical.
In one embodiment, in the group that the optional free ring hexyl of Ar, phenyl, tolyl, methylethyl phenyl, p-methoxy-phenyl, cyclohexyl phenyl, chloro-phenyl-, bromophenyl, phenyl and benzyl phenyl are formed.
The instance of above-mentioned aromatics or alicyclic compound can comprise cyclohexyl (methyl) propenoate; Ethyl phenol oxygen base (methyl) propenoate; 2-ethylmercapto group phenyl (methyl) propenoate; 2-ethylamino phenyl (methyl) propenoate; Phenyl (methyl) propenoate; Benzyl (methyl) propenoate; 2-phenylethyl (methyl) propenoate; 3-phenyl propyl (methyl) propenoate; 4-phenyl butyl (methyl) propenoate; 2-2-aminomethyl phenyl ethyl (methyl) propenoate; 2-3-aminomethyl phenyl ethyl (methyl) propenoate; 2-4-aminomethyl phenyl ethyl (methyl) propenoate; 2-4-propyl group phenylethyl (methyl) propenoate; 2-(4-(1-methylethyl) phenyl) ethyl (methyl) propenoate; 2-(4-p-methoxy-phenyl) ethyl (methyl) propenoate; 2-(4-cyclohexyl phenyl) ethyl (methyl) propenoate; 2-(2-chloro-phenyl-) ethyl (methyl) propenoate; 2-(3-chloro-phenyl-) ethyl (methyl) propenoate; 2-(4-chloro-phenyl-) ethyl (methyl) propenoate; 2-(4-bromophenyl) ethyl (methyl) propenoate; 2-(3-phenyl) ethyl (methyl) propenoate; 2-(4-benzyl phenyl) ethyl (methyl) propenoate and their combination.Particularly, can use cyclohexyl (methyl) propenoate, ethyl phenol oxygen base (methyl) propenoate, (methyl) phenyl acrylate or their combination, but be not limited thereto.
Can be simple function group unsaturated monomer (D2) with the monomer of above-mentioned aromatics or alicyclic acrylic compound copolymerization.Simple function group unsaturated monomer (D2) can comprise; But be not limited to ester, acid amides, nitrile, glycidyl allyl ether, SY-Monomer G and the styrene monomer of (methyl) propenoate, unsaturated carboxylic acid, acid anhydrides, hydroxyl, they can use separately or use with mixture.
Particularly, the instance of above-mentioned simple function group unsaturated monomer can include, but are not limited to alkyl methacrylate, like TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate and NSC 20956; Alkyl acrylate is like methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi and ethyl acrylate; Unsaturated carboxylic acid is like vinylformic acid and methylacrylic acid; Acid anhydrides is like maleic anhydride; The propenoate of hydroxyl is like vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxypropyl acrylate and vinylformic acid direactive glyceride; Acid amides is like acrylic amide and USAF RH-1; Nitrile is like vinyl cyanide and methacrylonitrile; Glycidyl allyl ether; SY-Monomer G; Styrenic is like alpha-methyl styrene; Or their combination.Particularly, can use alkyl methacrylate or alkyl acrylate, but be not limited thereto.
The instance of modification (methyl) PEMULEN TR2 can comprise the multipolymer of TEB 3K and phenyl methacrylate.
Modification (methyl) PEMULEN TR2 can come polymerization with mass polymerization, emulsion polymerization or the suspension polymerization of routine.
Modification (methyl) PEMULEN TR2 can have the specific refractory power bigger than common XPA.That is to say that modification (methyl) PEMULEN TR2 can have the specific refractory power identical with polycarbonate resin.In one embodiment, modification (methyl) PEMULEN TR2 can have 1.495 to 1.590 specific refractory power.When modification (methyl) PEMULEN TR2 has the specific refractory power of increase, promptly when modification (methyl) PEMULEN TR2 has the specific refractory power in the above-mentioned scope, can improve the consistency and the transparency, make it can with the polycarbonate resin blend well.Therefore, polycarbonate resin has the scratch resistance and the high transparent of improvement, and highly colored.In one embodiment, this specific refractory power can be 1.51 to 1.59.
In one embodiment, modification (methyl) acrylic copolymer resin (D) can have 5,000 to 25, the weight-average molecular weight of 000g/mol.In this scope, poly carbonate resin composition can demonstrate high transparent.Particularly, this weight-average molecular weight can be 7,000 to 20,000g/mol.
In another embodiment, modification (methyl) acrylic copolymer resin (D) can have 25,000 to 50, the weight-average molecular weight of 000g/mol.In this scope, poly carbonate resin composition can demonstrate translucency, thereby is used to not require the material of high transparent.
Can optionally add above-mentioned modification (methyl) acrylic copolymer resin (D) to matrix resin.The content of modification (methyl) acrylic copolymer resin (D) in matrix resin can be 40wt% or lower.In this scope, can obtain excellent consistency, shock resistance and scratch resistance.In one embodiment, the content of modification (methyl) PEMULEN TR2 in matrix resin can be 10 to 30wt%.
In one embodiment, the weight ratio that polycarbonate-polysiloxane copolymer (B) and modification (methyl) acrylic copolymer resin (D) can 3: 1 to 1: 1 is mixed.In this scope, can obtain the performance balance of the excellence between shock resistance, scratch resistance, the transparency, thermotolerance, flowability and the tinctorial property.
(E) other additive
Poly carbonate resin composition can further comprise the fatty acid amide surface treatment agent.
The fatty acid amide surface treatment agent can be C15 to C30 aliphatic alkyl acid amides.The instance of above-mentioned fatty acid amide surface treatment agent can include, but are not limited to stearylamide, mustard acid amides (erucamide), oleylamide and mountain Yu acid amides (behenamide).
Based on the matrix resin of 100 weight parts, the content of above-mentioned fatty acid amide surface treatment agent can be 0.1 to 5 weight part.In this scope, can obtain excellent anti-damageability.
Above-mentioned poly carbonate resin composition can further comprise syndiotactic PS.
The instance of syndiotactic PS can include, but are not limited to PS, gathers (p-methylstyrene), gathers (vinyl toluene), gathers (to t-butyl styrene), gathers (to chloro-styrene), gathers (m-chlorostyrene), gathers (to fluorostyrene) and gather (to phenylcyclohexane ethene).
Based on the matrix resin of 100 weight parts, the content of syndiotactic polystyrene can be 5 weight parts or lower, preferred 1 to 5 weight part.In this scope, this resin can have the shock resistance of improvement.
Said resin combination can further comprise additive; Like dripping inhibitor, antiseptic-germicide, thermo-stabilizer, inhibitor, releasing agent, photostabilizer, inorganic additives, tensio-active agent, coupling agent, softening agent, mixture, stablizer, lubricant, static inhibitor, toning agent, flame-proofing agent, weather resisting agent, tinting material, UV absorption agent, UV blocking agent, fire retardant, filler, nucleator, adhesion auxiliary agent, tackiness agent, or their combination.
The instance of dripping inhibitor can comprise the tetrafluoroethylene terephthalate.Yet, when adding dripping inhibitor, can reduce the transparency.Therefore, based on the matrix resin of 100 weight parts, dripping inhibitor content can be 2 weight parts or lower, preferred 1.5 weight parts or lower, more preferably 1 weight part or lower, and further more preferably 0.8 weight part or lower.When its content surpasses this scope, can reduce the transparency.
The instance of inhibitor can comprise phenolic antioxidant, phosphite antioxidant, thioether inhibitor or amine inhibitor.The instance of releasing agent can comprise metal-salt, montanic acid ester type waxes or the polyethylene wax of fluoropolymer, silicone oil, stearic metal-salt, montanic acid.The instance of weathering resistance can comprise UVNUL MS-40 or amine weather resisting agent.The instance of tinting material can comprise dyestuff or pigment.The instance of UV blocking agent can comprise titanium oxide (TiO2) or carbon black, and wherein carbon black can be conductive carbon black, like graphited carbon, furnace black, acetylene black and Ketjen black (ketchen black), but is not limited thereto.The instance of filler can comprise spun glass, thomel, silicon-dioxide, mica, aluminum oxide, clay, lime carbonate, calcium sulfate or glass microballon.The instance of nucleator can comprise talcum or clay.
Above-mentioned additive can suitably add, as long as the performance of poly carbonate resin composition variation not.Based on the poly carbonate resin composition of 100 weight parts, content of additive can be 40 weight parts or lower.In one embodiment, content of additive can be 0.1 to 30 weight part.
Above-mentioned poly carbonate resin composition has excellent scratch resistance and anti-damageability; It is anti-fine scratch; Realize the high gloss texture, kept the transparency simultaneously, had the excellent properties balance between color rendition property, shock resistance, thermostability, gloss, scratch resistance and the transparency.In addition, polycarbonate compositions is suitable to uncoated material.In addition, when requiring high gloss and uncoated product with above-mentioned poly carbonate resin composition manufacturing, do not need coating procedure, thereby significantly reduce cost and eco-friendly effect is provided.
Poly carbonate resin composition has excellent intrinsic shock strength, thereby need not comprise impact-reinforcement or rubber components.Rubber components comprises the multipolymer of modified rubber, like ABS, MABS, AES and AAS.When above-mentioned resin combination comprises impact-reinforcement or rubber element, can reduce its transparency.
Above-mentioned poly carbonate resin composition can be used any currently known methods preparation of preparation resin combination.For example, mixing said ingredients and other additive melt extrude in forcing machine, and form particle simultaneously.
Another aspect of the present invention provides a kind of moulded product that uses above-mentioned poly carbonate resin composition.That is, above-mentioned poly carbonate resin composition can be through various technologies, like injection moulding, blowing, extrusion molding, and thermoplastic, form moulded product.Particularly, said composition is used for moulded product, for example requires shock resistance, scratch resistance, the transparency and stable on heating electricity or electronic component and automotive components.
Below will explain formation of the present invention and function in more detail with reference to following examples.Provide these embodiment only to be used for illustrative purposes and also be understood as restriction the present invention never in any form.
Embodiment
The specification specified of used component is following in embodiment and the Comparative Examples.
(A) polycarbonate resin
Use that Cheil Industries Inc. produces 310 ℃ with 1.2kgf under have the Infino of the MFI of 8g/10min.
(B) polycarbonate-polysiloxane copolymer
The Tarflon that uses Idemitsu Chemicals to produce.
(C) polyoxyethylene alkyl aryl radical siloxane
(C-1) the TSF437 that uses GE Toshiba Silicones to produce with 1.499 specific refractory poweres.
(C-2) the SILRENM1010 that uses Korea S Biogen ltd to produce with 1.529 specific refractory poweres.
The fatty ester Unister H-476 that (C ') uses NOF company to produce.
(the amino-terminated ZGK 5 XF42-C2999 that C ") uses that GE Toshiba Silicones produces with specific refractory power of 1.406.
(D) (methyl) acrylic copolymer resin of modification
The weight-average molecular weight of the phenyl methacrylate preparation of TEB 3K and the 35wt% of use through common suspension polymerization 65wt% is 20, the multipolymer of 000g/mol.
(E) fatty acid amide surface treatment agent
The oleylamide Finawax OK that uses Fine Chemicals Inc. to produce.
(F) syndiotactic PS
The syndiotactic polystyrene Zarex 130ZC that uses Idemitsu Chemicals to produce.
Embodiment 1 to 10 and Comparative Examples 1 to 6
Mix above component according to the listed composition of table 1, and add 0.2 parts by weight of carbon black, extrude with 45 Φ twin screw extruders subsequently to it, and in 100 ℃ moisture eliminator dry 4 hours to make particle.This particle 80 ℃ of dryings 4 hours, and is carried out injection moulding with preparation ASTM dumbbell shaped sample with 6 ounces of injection moulding machines, and barrel temperature is 210 ℃ to 230 ℃, and die temperature is 100 ℃, and the molded cycle is 30 seconds.The physicals of measuring these samples is following, and the result is shown in table 1 to the table 3.
(1) blackness
Measure the L value according to ASTM D1925 method with Konica Minolta CCM.
(2) otch-IZOD shock strength
Using thickness according to ASTM D256 method is 1/8 " sample determination otch-IZOD (kgfcm/cm).
(3) ball-type scratches profile (BSP) width
Use to have diameter and sample is applied the load of 1kgf, and on sample, form cut, observe profile subsequently, and measure with surface profiler and to scratch width (μ m) with the speed of 75mm/min as the wolfram varbide stylus point of the ball point of 0.7mm.
(4) die orifice impacts
Behind injection moulding pin mark 2T sample, as the metal tip free-falling of 10mm the die bearing of sample is applied the load of 2kgf through using diameter, thereby measure the shock resistance (%) on the die bearing.
(5) anti-damageability
With ultra-fine fibre cloth friction sample 500 times, observe outward appearance with abrasion polishing trier subsequently.
1: best
3: good
5: medium
7: poor
9: the poorest
Table 1
As shown in table 1, according to the poly carbonate resin composition that comprises the polyoxyethylene alkyl aryl radical siloxane of embodiment 1 to 3 with have the remarkable scratch resistance that has improved according to Comparative Examples 1 and 2.
Table 2
As shown in table 2, according to the poly carbonate resin composition that comprises the polyoxyethylene alkyl aryl radical siloxane of embodiment 4 to 6 with compare anti-damageability according to Comparative Examples 3 with those compsns of 4 with remarkable improvement.Fig. 1 shows embodiment 4 and the sample photo of Comparative Examples 4 after the die orifice Impact Test.As shown in Figure 1, for Comparative Examples 4, comprise that the fatty ester lubricant replaces the poly carbonate resin composition of siloxane surface treatment agent to have the shock resistance that significantly reduces.
Table 3
As shown in table 3, when the amount increase of surface treatment agent, anti-damageability further improves.In addition,, have the blackness of reduction, cause its degraded appearance with the poly carbonate resin composition of siloxanes preparation with low-refraction for Comparative Examples 5.
Although Wen Zhongyi discloses some embodiments, what it will be understood by those skilled in the art that is only with the mode of explanation these embodiments to be provided, and can carry out various modifications, change and displacement and do not deviate from the spirit and scope of the present invention.Therefore, scope of the present invention should only be limited accompanying claims and Equivalent thereof.
Claims (15)
1. a poly carbonate resin composition has high gloss and shock resistance and good surface properties, and said compsn comprises:
The matrix resin that comprises polycarbonate resin (A) and polycarbonate-polysiloxane copolymer (B) of 100 weight parts; With
0.1 polyoxyethylene alkyl aryl radical siloxane (C) with specific refractory power of 1.42 to 1.59 to 10 weight parts.
2. poly carbonate resin composition according to claim 1, wherein said polyoxyethylene alkyl aryl radical siloxane (C) has the weight-average molecular weight of 400g/mol to 1000g/mol.
3. poly carbonate resin composition according to claim 1, wherein said polyoxyethylene alkyl aryl radical siloxane (C) is 25 ℃ of viscosity with 20mPa.s to 120mPa.s.
4. poly carbonate resin composition according to claim 1, wherein said matrix resin comprise 1 to 99wt% said polycarbonate resin (A) and 1 to 99wt% said polycarbonate-polysiloxane copolymer (B).
5. poly carbonate resin composition according to claim 1, wherein said polycarbonate-polysiloxane copolymer (B) comprise 1 to 99wt% polycarbonate block and 1 to 99wt% polysiloxane block.
6. poly carbonate resin composition according to claim 1, wherein said matrix resin further comprise 40wt% or modification still less (methyl) acrylic copolymer resin.
7. poly carbonate resin composition according to claim 6, wherein said modification (methyl) acrylic copolymer resin has 1.495 to 1.590 specific refractory power.
8. poly carbonate resin composition according to claim 1, wherein said modification (methyl) acrylic copolymer resin has 5,000g/mol to 50, the weight-average molecular weight of 000g/mol.
9. poly carbonate resin composition according to claim 1, wherein said modification (methyl) acrylic copolymer resin are aromatics or alicyclic (methyl) acrylic ester polymer.
10. poly carbonate resin composition according to claim 9, wherein said modification (methyl) acrylic copolymer resin are the polymkeric substance of simple function group unsaturated monomer (D2) that comprises the aromatics with structure shown in general formula 4 or 5 or alicyclic (methyl) propenoate (D1) and 0 to 80wt% of 20wt% to 100wt%:
[general formula 4]
Wherein m representes 0 to 10 integer, and X is selected from the group of being made up of cyclohexyl, phenyl, tolyl, methylethyl phenyl, propyl phenyl, p-methoxy-phenyl, cyclohexyl phenyl, chloro-phenyl-, bromophenyl, phenyl and benzyl phenyl and
[general formula 5]
Wherein m representes 0 to 10 integer, and Y representes oxygen or sulphur, and Ar is selected from the group of being made up of cyclohexyl, phenyl, tolyl, methylethyl phenyl, p-methoxy-phenyl, cyclohexyl phenyl, chloro-phenyl-, bromophenyl, phenyl and benzyl phenyl.
11. comprising, poly carbonate resin composition according to claim 10, wherein said simple function group unsaturated monomer (D2) be selected from least a in the group of forming by ester, acid amides, nitrile, glycidyl allyl ether, SY-Monomer G and the styrene monomer of (methyl) propenoate, unsaturated carboxylic acid, acid anhydrides, hydroxyl.
12. poly carbonate resin composition according to claim 1, wherein based on the said matrix resin of 100 weight parts, said poly carbonate resin composition further comprises the fatty acid amide surface treatment agent of 0.1 to 5 weight part.
13. poly carbonate resin composition according to claim 1, wherein based on the said matrix resin of 100 weight parts, said poly carbonate resin composition further comprises 5 weight parts or syndiotactic polystyrene still less.
14. poly carbonate resin composition according to claim 1, wherein said resin combination further comprise at least a additive that is selected from the group of being made up of antiseptic-germicide, thermo-stabilizer, inhibitor, releasing agent, photostabilizer, inorganic additives, tensio-active agent, coupling agent, softening agent, mixture, stablizer, lubricant, static inhibitor, toning agent, flame-proofing agent, weather resisting agent, tinting material, UV absorption agent, UV blocking agent, fire retardant, filler, nucleator, adhesion auxiliary agent and tackiness agent.
15. a moulded product comprises each described poly carbonate resin composition in the claim 1 to 14.
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2455426B1 (en) | 2021-01-06 |
| US8829091B2 (en) | 2014-09-09 |
| KR101340539B1 (en) | 2014-01-02 |
| CN102558812B (en) | 2015-01-28 |
| EP2455426A1 (en) | 2012-05-23 |
| KR20120055277A (en) | 2012-05-31 |
| US20120129993A1 (en) | 2012-05-24 |
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